Stability of the Nanoporous Bismuth Oxide Photoanodes for Solar Water Splitting

Chitrada, Kalyan; Raja, Krishnan S.

doi:10.1007/978-1-4939-1628-3_9

Materials and Processes for Solar Fuel Production

2014

DOI: 10.1007/978-1-4939-1628-3_9

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Stability of the Nanoporous Bismuth Oxide Photoanodes for Solar Water Splitting

Kalyan Chitrada

Krishnan S. Raja

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Cited by 6 publications

(3 citation statements)

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“…25 Recently the present authors reported formation of nanoporous anodic oxide of bismuth by a facile anodization process. [26][27][28][29] The * Electrochemical Society Member. z E-mail: chit7390@vandals.uidaho.edu; kalyanchitrada@gmail.com nanoporous β-Bi 2 O 3 showed relatively high initial photocurrent density, yet the photocurrent decayed upon continuous illumination.…”

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Enhanced Performance of β-Bi₂O₃by In-Situ Photo-Conversion to Bi₂O₃-BiO_2-xComposite Photoanode for Solar Water Splitting

Chitrada

Gakhar

Chidambaram

et al. 2016

J. Electrochem. Soc.

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Ordered nanoporous bismuth oxide layer consisting of metastable β-Bi 2 O 3 phase that showed n-type semiconductivity was synthesized by a simple electrochemical anodization of bismuth substrate. When the anodic nanoporous β-Bi 2 O 3 samples were tested as photoanodes for solar water splitting application in 0.5 M Na 2 SO 4 (pH:5.8), and 1 M KOH (pH:13.7), the photocurrent decayed continuously with time from an initial value of 0.95 mA/cm 2 under 1-sun illumination at a bias potential of 1.5 V RHE . Accumulation of photo generated holes at the photoanode/ electrolyte was attributed to the photocurrent decay. Addition of methanol as sacrificial hole scavenger was not found to be effective for the bismuth oxide photoanodes. When hydrogen peroxide was added to the 0.5 M Na 2 SO 4 electrolyte, the photocurrent density increased to ∼4 mA/cm 2 and was stable for more than 1 h of illumination of AM1.5 global light at 1.5 V RHE . Addition of hydrogen peroxide to the 1 M KOH solution showed a gradual increase in the photocurrent density for the first 300 seconds of light illumination to a maximum value of ∼10 mA/cm 2 at 0.65 V RHE and then it decreased continuously. The high photocurrent density of nanoporous β-Bi Bismuth based mixed oxides such as BiVO 4 , BiFeO 3 , BiWO 6 , Bi 3 NbO 7 , and Bi 2 MoO 6 are being actively investigated as promising high efficiency photocatalysts for solar water splitting applications. 1-11These bismuth based oxides show predominantly n-type semiconductivity and therefore function as photoanodes in the photoelectrochemical water splitting process. A significant amount of literature is available on the photoelectrochemical behavior of bismuth based ternary oxides, however very few studies have reported the performance of the binary Bi 2 O 3 which is the elementary constituent of the advanced bismuth mixed oxides. The photocatalytic behavior of the bismuth based oxides is well documented and the factors that limit their performance is well understood. Most importantly they exhibit low catalytic activity for oxygen evolution, which results in hole accumulation at the electrode/electrolyte interface. In order to overcome this limitation, a thin layer of oxygen evolution catalysts such as Co-Pi, FeOOH, Ni(OH) 2 or CoPO 4 is usually coated on the photoanodes.12-17 The binary and ternary bismuth oxides show more or less similar electronic structures, where the valence bands of both binary Bi 2 O 3 , and mixed bismuth oxides are considered to be formed by O-2p and Bi-6s orbitals. 18,19 The top of the Bi-6s orbital is positioned at more negative potential than that of O-2p. [20][21][22] The conduction band of Bi 2 O 3 is predominantly formed by Bi-6p orbitals. Whereas, the conduction band of mixed bismuth oxide is determined by the d-orbitals of transitions metals present in the mixed oxide. Bismuth oxide shows enhanced mobility of charge carriers because of its well-dispersed valence bands and it has high refractive index and large dielectric constant due to lone electron pairs of Bi(III) 6s 2 that...

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mentioning

confidence: 99%

“…25 Recently the present authors reported formation of nanoporous anodic oxide of bismuth by a facile anodization process. [26][27][28][29] The * Electrochemical Society Member.…”

mentioning

confidence: 99%

Enhanced Performance of β-Bi₂O₃by In-Situ Photo-Conversion to Bi₂O₃-BiO_2-xComposite Photoanode for Solar Water Splitting

Chitrada

Gakhar

Chidambaram

et al. 2016

J. Electrochem. Soc.

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“…21 The metastable β-Bi 2 O 3 , that is stable in the temperature range of 650-303 • C, could be stabilized at room temperature by doping with cations that introduce excess oxygen sublattices within the tunnel structures of the β-Bi 2 O 3 . 22,23 So far, many different nanostructures of β-Bi 2 O 3 photocatalysts have been successfully prepared by techniques like magnetron sputtering, 24 sol-gel, 25 spin coating, 26 solution based, 27,28 electrochemical anodization, [29][30][31][32][33][34][35][36][37][38] electrospinning, 39 vapor deposition, 40 but in contrast, the photoelectrochemical testing of β-Bi 2 O 3 has not received much attention.…”

mentioning

confidence: 99%

Enhanced Photoelectrochemical Performance of Anodic Nanoporous β-Bi₂O₃

Chitrada

Raja

Gakhar

et al. 2015

J. Electrochem. Soc.

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Bismuth oxide has well-dispersed valence bands that show enhanced mobility of charge carriers, high refractive index, and large dielectric constant. These properties are attractive for photo catalysis. Thin films of bismuth oxide containing vertically oriented and uniformly distributed nanopores of controllable dimensions were synthesized by a simple electrochemical anodization of a bismuth metal substrate in citric acid solution at 3-60 V. Annealing the anodic nanoporous Bi 2 O 3 at 200 • C for 2 h resulted in stabilization of the metastable β-Bi 2 O 3 phase at room temperature. The nanoporous anodic oxides showed an energy bandgap of 2.48 eV, and n-type semiconductivity. Scanning electron microscopy and electrochemical impedance spectroscopy results suggested a dual layered structure of the anodic oxide with a nanoporous outer layer and a planar inner layer. Thickness of the inner layer predominantly influenced the impedance of the anodic oxide. Under simulated 1-sun intensity, a maximum photo current density of 0.97 mA/cm 2 was observed in 1 M KOH at a potential of 1.53 VRHE for the sample anodized at 10 V. A positive shift in the flatband potential upon illumination suggested accumulation of photo generated holes due to low catalytic activity of the anodic bismuth oxide for oxygen evolution reaction. The observed photo current density of the nanoporous anodic oxide of bismuth was an order of magnitude higher than that of the planar anodic oxide, and twice that of thin film β-Bi 2 O 3 prepared by reactive sputtering.Synthesis of ordered arrays of nanoporous and nanotubular oxides of Al, Ti, and other valve metals has been investigated extensively because of their potential applications in solar energy conversion, energy storage, photocatalysts, sensors, and as templates for nanowire growth. 1-8 Enhanced photo catalytic, electrical, and electrochemical properties were reported for the nanoporous and nanotubular oxides, particularly TiO 2 and Fe 2 O 3 , when compared to their bulk crystalline counterparts. 9-14 Bismuth is different from regular valve metals such as Al, Ti, Nb etc., because of its semi-metallic nature and high atomic number with the electron configuration [Xe]4f 14 5d 10 6s 2 6p 3 . The large nuclear charge of bismuth increases the velocity of the 1s electrons to such an extent that the relativistic effect becomes significant which increases the mass of 1s electron by 26% and decreases the Bohr radius by 20%. Furthermore, the 6s electrons are less available for bonding. The normally degenerate p orbitals are split in to one spherically symmetric p 1/2 and two doughnut shaped p 3/2 orbitals because of the high degree of spin-orbit interaction. Since the p 3/2 orbitals have higher energy than p 1/2 , the p 3/2 electron is removed during first ionization of Bi resulting in an electron configuration of Bi(I) as 6s 2 6p 2 1/2 6p 0 3/2 . The major relativistic effects of bismuth are its lowest tendency to form a hybrid orbital and increasing tendency to form pyramidal structure. 15 The lone electron pa...

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Millettia pinnata plant pod extract-mediated synthesis of Bi2O3 for degradation of water pollutants

Meena

Surela

Saini

et al. 2022

Environ Sci Pollut Res

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Stability of the Nanoporous Bismuth Oxide Photoanodes for Solar Water Splitting

Cited by 6 publications

References 36 publications

Enhanced Performance of β-Bi₂O₃by In-Situ Photo-Conversion to Bi₂O₃-BiO_2-xComposite Photoanode for Solar Water Splitting

Enhanced Performance of β-Bi₂O₃by In-Situ Photo-Conversion to Bi₂O₃-BiO_2-xComposite Photoanode for Solar Water Splitting

Enhanced Photoelectrochemical Performance of Anodic Nanoporous β-Bi₂O₃

Millettia pinnata plant pod extract-mediated synthesis of Bi2O3 for degradation of water pollutants

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Product

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Stability of the Nanoporous Bismuth Oxide Photoanodes for Solar Water Splitting

Cited by 6 publications

References 36 publications

Enhanced Performance of β-Bi2O3by In-Situ Photo-Conversion to Bi2O3-BiO2-xComposite Photoanode for Solar Water Splitting

Enhanced Performance of β-Bi2O3by In-Situ Photo-Conversion to Bi2O3-BiO2-xComposite Photoanode for Solar Water Splitting

Enhanced Photoelectrochemical Performance of Anodic Nanoporous β-Bi2O3

Millettia pinnata plant pod extract-mediated synthesis of Bi2O3 for degradation of water pollutants

Contact Info

Product

Resources

About

Enhanced Performance of β-Bi₂O₃by In-Situ Photo-Conversion to Bi₂O₃-BiO_2-xComposite Photoanode for Solar Water Splitting

Enhanced Performance of β-Bi₂O₃by In-Situ Photo-Conversion to Bi₂O₃-BiO_2-xComposite Photoanode for Solar Water Splitting

Enhanced Photoelectrochemical Performance of Anodic Nanoporous β-Bi₂O₃